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Article Synopsis
  • A new method for adding alkynyl groups to certain carbon-hydrogen (C-H) bonds next to nitrogen in tertiary amines has been developed using alkynyl bromides and visible light.
  • This technique successfully coupled various types of secondary and tertiary amines with different alkynyl bromides, yielding 51 propargylamines with moderate to excellent results (31-80% yield).
  • The process likely works through a mechanism involving radical reactions, as indicated by early studies on how the reaction occurs.
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In this article, a practical and metal-free method for the synthesis of poly-functionalized 3-selenyl/sulfenyl/telluriumindoles from -alkynyl arylamines has been achieved. In this protocol, the formation of selenenyl chloride, sulfenyl chloride or tellurenyl chloride is considered as the key intermediate and the 3-selenyl/sulfenyl/telluriumindoles can be obtained in good to excellent yields. Furthermore, the product 2-phenyl-3-(phenylselanyl)-1-tosyl-1-indole can be selectively oxidized to compounds 2-phenyl-3-(phenylseleninyl)-1-tosyl-1-indole and 2-phenyl-3-(phenylselenonyl)-1-tosyl-1-indole in good yields.

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Stepwise synthesis of 2,6-difunctionalized ethyl pyrazolo[1,5-]pyrimidine-3-carboxylate site-selective cross-coupling reactions: experimental and computational studies.

Org Biomol Chem

December 2022

Laboratoire de Physico-Chimie des Matériaux et des Electrolytes pour l'Energie (PCM2E), EA 6299. Université de Tours, Faculté des Sciences et Techniques, Avenue Monge Faculté des Sciences, Parc de Grandmont, 37200 Tours, France.

A variety of novel disubstituted 2-(alknyl, aryl and arylamine)-6-alkynylpyrazolo[1,5-]pyrimidine derivatives was prepared sequential site-selective cross-coupling reactions from 2,6-dibromopyrazolo[1,5-]pyrimidine 3. The regio-controlled Sonogashira-type coupling of 3 with a wide range of terminal alkynes proceeded smoothly with excellent selectivity in favor of the C6-position through careful adjustment of the coupling conditions, followed by the subsequent introduction of alkynyl, aryl or arylamine groups at the C2-position the Sonogashira, Suzuki-Miyaura and Buchwald-Hartwig coupling reactions, respectively. These promising results allow for further use and diversification of the chemically and biologically interesting pyrazolo[1,5-]pyrimidine scaffold.

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Synthesis of substituted 1,2-dihydroisoquinolines via Ni(ii) and Cu(i)/Ag(i) catalyzed double nucleophilic addition of arylamines to ortho-alkynyl donor-acceptor cyclopropanes (o-ADACs).

Org Biomol Chem

July 2021

Catalysis and Fine Chemicals Division, CSIR Indian Institute of Chemical Technology, Tarnaka, Hyderabad - 500007, India. and Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, UP, India.

A concise approach for the synthesis of substituted 1,2-dihydroisoquinolines via double nucleophilic addition of primary arylamines to ortho-alkynyl donor-acceptor cyclopropanes (o-ADACs) in the presence of a catalytic Ni(ClO)·6HO and CuI/AgOTf system has been developed. Further applying this protocol, some of the derived malonates were converted into the corresponding monoesters under Krapcho decarboxylation reaction conditions. Thereafter, these esters were transformed into the respective acids and alcohols.

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Intramolecular benzoallene-alkyne cycloaddition initiated by site-selective S2' reaction of epoxytetracene en route to π-extended pyracylene.

Chem Commun (Camb)

September 2019

Department of Applied Chemistry for Environment, School of Science and Technology, Kwansei Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan.

A hydrogen halide promoted cascade reaction of epoxytetracene to afford halo-benzoindenotetracene including a benzoallene intermediate was developed. The remaining two alkynyl groups in benzoindenotetracene were further reacted with norbornadiene or arylamine through transition metal-catalyzed cyclization to give π-extended pyracylene derivatives.

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